Formaldehyde-epoxidized polyepoxidepolyamine precondensate altering resins and process for preparing them



United States, Patent 3,336,247 FORMALDEHYDE EPOXIDIZED POLYEPOXIDE-POLYAMINE PRECONDENSATE A L T E R I N G RESINS AND PROCESS FOR PREPARINGTHEM John C. Williams, Meriden, Conn., assignor to Hawley ProductsCompany, St. Charles, Ill., a corporation of Delaware No Drawing. FiledNov. 17, 1964, Ser. No. 411,707

. 14 Claims. (Cl. 260 -9) This application is a continuation-in-part ofmy copending application Ser. No. 129,516, filed Aug. 7, 1961 and nowabandoned.

This invention relates to a new class of resins and more particularly toa new class of reactive cationic water soluble resins possessing greatutility in the processing of normally anionic fibers, such as, forexample, cellulose, in the manufacture of paper, moldings containingsuch fibers, wall board, and other fibrous articles.

One of the objects of the invention is to provide a new and improvedresinous material which is substantive to water dispersed anionicfibers, especially cellulose fibers, and which can be added in thebeater to make the processed fibrous article water repellent.

Another object of the invention is to provide a resinous material whichcan be used in the manner described without the use of alum, therebyavoiding the well known deleterious effects of alum which occur on theaging of a cellulose product.

Another object is to provide a Water dispersed thermosetting resin whichmay be applied to paper and paper products as a tub size. This size notonly acts as a binding and strengthening agent but also improvessubsequent wetting and bonding of solvent based adhesives. Still anotherobject is to provide a beater treatment of cellulose fibers, alone or inadmixture with other fibers, with a resinous material which will givethe resultant dried and cured felted product good wet strength.

Still another object of the invention is to provide a cationic resinouscolloid Which will' both neutralize the negative charge on waterdispersed anionic fibers, such as cellulose, and attach lipophilicgroups to assist in the deposition ofhydrocarbon solvent soluble resinsand/or their solvent solutions on the fiber.

A further object is to provide a cationic resinous colloid which willdeposit on and chemically react with anionic fibers, such as cellulose,in the water dispersed state. In this objective is included thepreparation of fiber slurries in which one or more treated fibervarieties will accept oil or organic solvent soluble resins and otheruntreated fibers will reject them.

An additional object of the invention is to improve the colorability anddye-ability of anionic fibers, such as, for example, cellulose, with oilsoluble dyes or colored solvent soluble resins.

Another object of the invention is to provide water soluble cationicresins substantive to and reactive with water swollen cellulose fiberswhich carry and afiix lipophilic molecular regions so that the fiberswhen used as moist or dry filters will wet with and retain largequantities of tars or oily materials. Such fibers are useful in makingcigarette filters.

Another important object of the invention is to alter the wettability ofcellulose and other anionic fibers in aqueous slurries so that suchfibers will be Wet by catalyzed unsaturated organic (ethenoid) monomericmolecules and readily undergo graft polymerization.

A further object is to provide a process of chemically attachingunsaturated groups to anionic fibers, such as cellulose, so that theycan copolymerize with unsaturated organic (ethenoid) monomericmolecules. Other objects will appear hereinafter.

The resins provided in accordance with the invention can be described asepoxidized precondensates reacted with formaldehyde.

It is known in the art that precondensates which have been described aswater soluble epoxy amine resins can be prepared by reacting analiphatic polyamine with a resinous epoxide. These precondensates arewater soluble and form water soluble salts with acids. Suchprecondensates can be used as starting materials for the purpose of theinvention by further epoxidizing them. The resultant epoxidizedprecondensate is then further reacted with formaldehyde to produce aproduct having novel and useful properties as hereinafter described.

In the preferred practice of the invention a polyepoxide is reacted witha polyamine containing at least two nitrogen atoms with active hydrogenatoms and at least four carbon atoms in the polyamine and the reactionis carried out with proportions of the reactants such that there are asufiicient number of reactive amino groups to react with at least twoepoxide groups in the polyepoxide. For example, one suitable polyepoxideis a diepoxide having the following formula This is a diepoxide made byreacting epichlorhydrin with 4,4'-dihydroxydiphenyldimethylmethane. Inorder to make a precondensate for the purpose of this invention, onemole of this diepoxide is reacted with two moles of a poly-amine havingtwo primary amino groups as, for example, diethylenetriamine. Thisproduces a water soluble precondensate which is also soluble in diluteacids. The resultant precondensate is then mixed with an additionalquantity of the diepoxide of Formula 1 and heated until incipientgelation occurs. At this point the reaction is short stopped by loweringthe pH. An acid, preferably hydrochloric acid, is usually added to theepoxidized precondensate solution to adjust the pH and stop thereaction. The result-ant product is an epoxidized precondensate of apolyepoxide and a polyamine.

The initial union of the polyepoxide with the polyamine is exothermicand very rapid. The reaction goes easily and a minimum of control isneeded. The products are thermoplastic and water soluble. In the secondstage, that is, the epoxidation of the precondensate, the reactionproceeds more slowly and it is normally desirable to control the secondreaction to produce water soluble resins and to stop the reaction bychilling and dilution prior to gelation or at the point where theviscosity has increased to incipient gelation. At the point of incipientgelation the resin will form a string on a glass stirring rod. Ifprecautions are taken to stop the reaction quickly, the epoxiidizedprecondensates can be formed in one step rather than two steps. It isdifiicult, however, to prevent gelling in a one step process due to theexothermic nature of the process.

Many dilferent types of polyepoxides may be employed as startinmaterials. One way of defining the polyepoxides is by the expressionepoxide equivalent. The epoxide equivalent is the number of grams ofresin containing one gram equivalent of epoxide. For the purpose of thisinvention the polyepoxide used in making the initial precondensateshould have an epoxide equivalent within the range of 43 to 1000. Thus,one commercial material having the general structure of Formula 1 whichcan be used for the purpose of the invention is a mixture of epoxidizeddihydroxydiphenyldimethylmethane having an average epoxide equivalent ofto 210 (Epon 828).

Other examples of suitable polyepoxides for the manufacture of theprecondensate are the following:

(a) Glycidyl ether resins, e.g., a compound having the following formula(b) Butadiene diepoxide having the formula o o (c) Epoxy Novolac resins,e.g., those having the following formula where n is a positive valuerepresenting a number of recurring monomeric units.

In general, the epoxides used in the invention are prepared bycondensing polyhydric compounds, especially dihydric phenols, withpolyfunctional halohydrins, especially epichlorhydrin and glyceroldichlorohydrin. The epoxide used in the first state of the process mustbe a polyepoxide, that is, it must contain two or more 1,2- epoxidegroups per molecule. In the second stage of the process, however,additional epoxide groups are added either by adding the samepolyepoxide or a different polyepoxide from that used in the first stageor by adding a substance capable of introducing 1,2-epoxide groups intothe molecule, such as, for example, epichlorhydrin or other glycerolhalohydrin.

The amine reactant must contain at least two amino nitrogen atoms havingreactive hydrogen atoms and should contain more than two carbon atomsbecause ethylene diamine has not been found to be satisfactory for thepurpose of the invention. The best results have been obtained withamines containing at least two primary amino groups and one or moresecondary amino groups. Typical examples of amines suitable for theinvention are propylene diamine, N-methyl propylene diamine, N-propylpropylene diamine, butylene, diamine, hexamethylene diamine,polyethylene polyamines, such as, for example, diethylene triamine,triethylene tetramine, tetraethylene pentamine, and polypropylenepolyamines, such as, for example, dipropylene triamine.

The first and second stages of the reaction are carried out underordinary alkaline conditions, the alkalinity being supplied by theamine.

In the first stage of the reaction the heat is normally supplied by theexothermic nature of the reaction but gentle heating to a temperature ofsay 120 F. is sometimes desirable to initiate the reaction. In general,the temperature during the first stage of the reaction is within therange of 120 F. to 350 F. In the second stage the reaction can becarried out at room temperature, that is, 70 F. but it is usuallypreferable to employ a compatible inert solvent, such as, for example,isopropyl alcohol, and where a solvent is used it is desirable to carrythe reaction out at a temperature below the boiling point of thesolvent. Of course, the solvent can be vaporized during the process andit can also be refluxed and returned to the reaction mixture. Forexample, where isopropyl alcohol is used as the solvent, a reactiontemperature of about 140 F. is normally employed. Another preferredsolvent is methyl ethyl ketone. Higher boiling solvents, such as xylene,have also been used and with such solvents the process can be carriedout at a higher temperature without evaporating the solvent. In general,however, it is preferred to use a water miscible solvent or one which isat least partly water miscible, otherwise the presence of the solventintroduces a cloudy appearance when the product is mixed with Water.

The time required to carry out the reaction is subject to variation. Inthe first stage the reaction is usually continued until the elevatedtemperature, due to the exothermic nature of the reaction, subsides. Inthe second stage the higher the temperature the shorter the time ofreaction. In other words, a longer period is required to carry out thereaction at 70 F. than at 140 F. and the time is determined by the timerequired to produce incipient gelation.

The reaction is stopped in the second stage by any one of a number ofexpedients, such as chilling, dilution and treatment with an acid.Treatment with an acid is the preferred method. Various acids may beused but it is preferable to use hydrochloric acid. The epoxidizedprecondensates can be characterized as being soluble in 2.5% by weighthydrochloric acid at 20 C. In connection with stopping the reaction itshould be noted that dilution with water will slow down the reaction buta reduction in pH by the addition of an acid is desirable to stop thereaction completely, otherwise a slow reaction will continue and aprecipitate will form in the aqueous slurry. The reduction in pH can bestopped while the product is still on the alkaline side, for example, atpH 8, or it can be continued until the product is on the acid side. ThepH of the product does not appear to be a factor in its subsequentreactions with cellulose and products having a pH from 2 to 12, wherethe pH has been adjusted with either caustic soda or hydrochloric acid,have reacted satisfactorily with cellulose.

The invention will be further illustrated by the following examples inwhich the quantities are stated in parts by weight unless otherwiseindicated.

EXAMPLE I 4.1 grams (0.04 mole) diethylene triamine was mixed with 7.8grams (0.02 mole) of Epon 828 (a diepoxide produced by Shell ChemicalCompany) and heated to F. The exotherm took the temperature to 250 F.When the material had cooled to 160 F. it was dissolved in 20 grams ofmethyl ethyl ketone and 4 grams of Epon 828 added. The solution was heldat 160 F. for /2 hour until the viscosity increase indicated incipientgelation. The solution was then stirred into 50 grams of water plus 8grams of 28% hydrochloric acid. The pH of this resin solution was 6.

EXAMPLE II The two stage reaction of Example I was carried out. Thesecond stage was (a) with no solvent; (b) with water; (c) with isopropylalcohol, and (d) with methyl ethyl ketone.

(a) 20 grams of tetraethylene pentamine (0.105 mole) was heated to F.with 20 grams of Epon 828 (0.056 mole) and allowed to go through theexotherm. This is Adduct A. After cooling to F., 10 grams of Epon 828was added and the reaction allowed to heat back to 158 F. to incipientgelation. At this time it was short stopped by diluting with 50 grams ofmethyl ethyl ketone plus 200 grams of water and 20 grams of 28% byweight hydrochloric acid.

(b) 40 grams of Adduct A was dissolved in 100 grams of Water and 10grams of Epon 828 added. The temperature was held at 140 F. with goodstirring for minutes during which time the solution thickened to a heavypaste. 100 grams of water was now added, with 20 grams of 28%hydrochloric a d. The solution was stir-red until reasonably clear. A sudge later formed in this material without afiecting its activity. Itwas observed that (a) tended to be a lower molecular weight resin than(b) because of the necessity for quick dilution before cross linking andinsolubility had set in.

(c) 40 grams of Adduct A dissolved in 50 grams isopropyl alcohol or 25grams methyl ethyl ketone (d) and treated with 10 grams Epon 828 washeated /2 hour at 160 F. until viscosity and slight gel formationindicated incipient gelation. This was then diluted with 200 grams ofwater, and 20 grams of 28% by weight hydrochloric acid. The solventsystems of (c) and (d) give clear solutions slightly less active thanthe water of (b). For safety in preparing large batches in openequipment the use of water is advantageous.

EXAMPLE III (a) 13 grams hexamethylene diamine was heated to 120 F. with20 grams of Epo11828 under a hood. There was a rapid evolution of heat.The liquid product was allowed to cool to 140 F. and 5 grams of Epon 828plus 25 grams of methyl ethyl ketone was added. After 5 minutes at 160F. the resin was dissolved in 100 grams of water and grams of 28%hydrochloric acid. The resin had a very good color.

(b) 5 grams of tetraethylene pentamine, 2 grams of phenylene diamine and7 grams of Union Carbide Plastics Company diepoxide ERL-2774 were heatedto 120 F. and allowed to go through the exotherm. This was dissolved in200 grams water and 12 grams of 28% hydrochloric acid.

(c) 14.6 grams of triethylene tetramine was heated with grams Epon 828and allowed to go through the exotherm. After cooling to 160 F. it wasdissolved in 50 grams methyl ethyl ketone and 10 grams Epon 828 added.This was held at 150 F. for approximately minutes until the solutionbecame of high viscosity. 200 grams water and 20 grams 28% by weighthydrochloric acid were now added.

EXAMPLE IV (a) 20 grams tetraethylene pentamine was heated with 4.3grams of butad-iene diepoxide and allowed to stand until heat was nolonger evolved. 3.0 grams of butadiene diepoxide was then added and thesolution heated to 160 F. until temperature and viscosity was risingsharply. 200 grams water and 20 grams 28% by weight hydrochloric acidwere then stirred in.

(b) Shell Chemical Epon 812 is an aliphatic diepoxide With an epoxideequivalent given as 140-160. 20 grams of tetraethylene pentamine wereheated with 10 grams of Epon 812 by the exothermic reaction and remainedfluid. This product was dissolved in 50 grams isopropyl alcohol and 7grams Epon 812 added. In 10 minutes at 140 F. viscosity had risen to apoint indicating imminent gelation and 200 grams of water plus 10 gramsof 28% by weight hydrochloric acid was added. This 12.5% solution was atpH 8.5 and was water thin.

(c) Resorcinol diglycidyl ether (RDGE) has a molecular weight of 222.218.0 grams (0.1 mole) of tetraethylene pentamine was heated with 11grams (0.05 mole of the RDGE). After exotherm and cooling to 140 F. thiswas dissolved in 50 grams isopropyl alcohol and 5 grams RDGE added. Thiswas held at 140 F. until bodied and diluted with 200 grams of water plus10 grams of 28% by weight hydrochloric acid.

(d) 18.0 grams of tetraethylene pentamine (0.1 mole) was heated with 10grams of Dow DEN 438 (0.017 mole), an epoxy Novolac resin having anaverage functionality of 3.3 and an epoxide equivalent of 179 (Formula4),. This made a heavy solution at 200 F.

At 160 F., 50 grams isopropyl alcohol was stirred in and the solutionheld at this temperature until the viscosity had risen. The solution wasthen'dissolved in 200 grams of water plus 10 grams 28% by weighthydrochloric acid.

EXAMPLE V Diepoxide (Grams) PerceutRNitrogen in These were heated to 120F. and allowed to stand until viscosity build-up started and then mixedwith 200 grams of water and 10 grams of 28% by weight hydrochloric acid.(a), (b), and (0) gave clear solutions. ((1), (e), and (f) were remadeusing 400 grams of water instead of 200 grams of water for dilution. Theresultant solutions were still opaque, but stable during the experiment.

EXAMPLE VI (a) 20 grams tetraethylene pentamine was reacted with 20grams of Epon 828 as in Example I. This was cooled to 140 F. anddissolved in 40 grams of methyl ethyl ketone. grams of water was addedand also 10 grams of 28% by weight hydrochloric acid. The pH was 9. 10grams of epichlorhydrin solution (50% in methyl etheyl ketone), wasslowly added to the adduct solution and the temperature brought to 160F. slowly and with good stirring. 10 grams more of the epichlorhydrinsolution was slowly added (exotherm). The solution was held at 160 F.until clear. At 20% concentration the solution gelled over night. Itcould be kept for a week by diluting to 5% cencentration with water.

EXAMPLE VII (a) 20 grams tetraethylene pentamine plus 30 grams Epon 828were dissolved in 50 grams of isopropyl alcohol and heated to 140 F.This solution then boiled gently from the heat of the reaction. After 5minutes the viscosity began to build up, and at the point that a 10 inchthread would spin oil the thermometer, and the viscosity wasapproximately 600 centipoises, the reaction was stopped by pouring in200 grams of water plus 20 grams 28% by weight hydrochloric acid.Viscosity was now 12 centipoises at F. and the solution at 14.4% solids.

Adding more isopropyl alcohol will allow a higher molecular weight buildup before the water-acid quench. This higher molecular weight promotesroom temperature adsorption and activity.

(b) 20 grams of tetraethylene pentamine and 30 grams of Epon 828 weredissolved in 100 grams of isopropyl alcohol, heated to F. and thenallowed to stand. The exotherm was not vigorous enough to heat this andthe mixture gradually cooled to 100 F. After two hours the solution hadthickened to about 1000 centipoises and had become slightly cloudy. Thiswas dissolved in 200 grams of water and 20 grams of 28% by weighthydrochloric acid. The pH was 8.5 and the viscosity 19 centipoises at 80F.

7 The foregoing Examples VII (a) and VII(b) illustrates a one stepprocess of making the epoxidized precon densates.

EXAMPLE VIII 20 grams of tetraethylene pentamine (0.10 mole) was mixedwith 20 grams (0.053 mole) of Epon 828 and heated to 130 F. The exothermcarried the temperature to 250 F. After cooling to 160 F. grams of Epon828 was added and heating continued to incipient gelation. The resin wasthen dissolved in 100 grams of water and grams of 28% by weighthydrochloric acid. The pH was 9.0.

In the foregoing examples it will be observed that the initial reactionbetween the polyepoxide and the polyamine is carried out underessentially anhydrous conditions. In the second stage, or later stagesof the reaction with additional polyepoxide, water can be added toassist in stopping the reaction. However, the addition of an acid isdesirable in order to stop the reaction completely. The mechanism of thereaction at this point is not clearly understood. It is possible thatthe acid reacts with the amino groups to form amine salts. The use ofhydrochloric acid is especially desirable because it does notsubstantially affect the properties of the resultant product. However,other dilute acids which ionize to give monovalent anions can be used,such as, for example, acetic acid, propionic acid, and the like.Sulfuric acid precipitates the resin. Phosphoric acid probably ionizesH++-H PO and hence precipitates the resin only to a slight extent.

An essential requirement of the product is that it be thermoplastic andsoluble in a dilute 2.5% by weight hydrochloric acid solution. In orderto meet this requirement it is necessary to maintain a balance betweenthe polyamine and the polyepoxide which may vary depending upon theparticular reactants. In general, it is desirable to use an amount of apolyamine such that there are at least two equivalents of reactive aminogroups for each epoxide equivalent in the first stage of the reactionand then to add in the second stage of the reaction 0.1 to 0.8equivalent of additional epoxide group. A larger quantity of epoxide canbe added in the second stage of the reaction, provided adequate dilutionis maintained. However, a point is eventually reached where the additionof a further quantity of the epoxide no longer enhances the affinity ofthe resin for cellulose fiber but, on the contrary, actually reducessuch afiinity. The resin preferably contains 16 to 70 epoxy groups per100 moles of resin. The nitrogen content is preferably at least 9% byweight.

The following section illustrates the results obtained by addingformaldehyde to the epoxidized precondensates previously described. Theformaldehyde is ordinarily added as formalin but para-formaldehyde orother formaldehyde-liberating compounds can be used. The addition of theformaldehyde produces resinous solutions which are more reactive thanthe epoxidized precondensates and which will react with cellulose atlower temperatures than the epoxidized precondensates. The formaldehydealso has a second function in that it introduces methylol groups intothe resin. These groups are hydrophilic and they act to prevent adsorbedlipophilic molecules from being dissolved off the fiber by solvent orliquid resin.

In the following examples in which the quantities are stated in parts byweight unless otherwise indicated, il' lustrations are given for thepreparation of epoxidized precondensates reacted with formaldehyde.

EXAMPLE IX The procedure was the same as that described in Example VIIIexcept that 20 grams of formalin was added to the resin solutionobtained in Example VIII. The addition of the formaldehyde contained inthe formalin solution causes polymerization of the resultant resin totake place at lower temperatures than the resin of Example VIII.

8 EXAMPLE X The procedure was the same as that of Example II(a) exceptthat 20 grams of formalin was added. Again the activity of the resin wasenhanced in the treatment of cellulose fiber.

EXAMPLE XI The procedure was the same as that of Example II(c) exceptthat 20 grams of formalin was added along with the 200 grams of waterand the 20 grams of 28% by weight hydrochloric acid. A resin of enhancedactivity was obtained.

EXAMPLE XII The procedure was the same as in Example III(b) except that14 grams of formalin was added to the resin solution of Example III(b).

EXAMPLE XIII The procedure was the same as in Example III(c) except that10 grams of formalin was added to the final resin solution of ExampleIII(c).

EXAMPLE XIV The procedure was the same as that described in ExampleIV(a) except that 10 grams of formalin was added to the final resinsolution of Example IV(a).

EXAMPLE XV The procedure was the same as that described in Example lV(b)except that 10 grams of formalin was added to the final resin solutionof Example IV(b). This caused the solution to form into a soft gel whichredispersed with 200 grams more water.

In the foregoing examples the amount of formaldehyde orformaldehyde-liberating substance employed is subject to variation butit is preferable to use at least one mole of HCHO per mole of epoxidizedprecondensate so as to introduce at least one methylol group into eachmolecule of the resin.

Epoxidized precondensates containing unsaturated reacting groups Inpracticing the invention it is possible to incorporate unsaturatedreactive groups into the epoxidized precondensates so that when theresultant resin solution is applied to cellulose or other materialunsaturated groups are available which are capable of copolymerizingwith ethenoid monomers, such as, for example, acrylonitrile, styrene,vinyl toluene, acrylic acid, methyl methacrylate, ethyl methacrylate,and other monomers containing an ethanoic linkage capable ofpolymerizing with the unsaturated group of the epoxide precondensateresin. One source of such unsaturated groups is allyl glycidyl ether butit will be understood that other substances containing both anunsaturated group and an epoxide group can be employed for the purposeof the invention.

This phase of the invention is illustrated by the following examples inwhich the quantities are stated in parts by weight.

EXAMPLE XVI 11.4 grams (0.1 mole) of allyl glycidyl ether were reactedwith 18.9 grams of tetraethylene pentamine (0.1 mole) by heating to 160F. The reaction evolved heat for 10* minutes and then Was held at 190 F.for another 10 minutes to insure complete reaction. This adduct wasallowed to cool to F. and 20 grams of Epon 828 stirred in. Thetemperature began to rise rapidly and at 180 F., 30 grams of isopropylalcohol was stirred in. 5 grams more of Epon 828 was added and thetemperature held at F. for 20 minutes until the viscosity had risen to300 centipoises at 80 F. The resin solution was dissolved in 500 gramsof water containing 20 grams of 28% hydrochloric acid. The resins ofthis example and of XVII were found to be excellent sizing agents forglass fiber to be used in polyester moldings.

9 EXAMPLE XVII The procedure was the same as that described in ExampleXVI except that 10 grams of formalin was added to the final resinsolution.

Epoxidized precondensates containing long chain fatty amines It has beenfound in the practice of the invention that the addition of a cationcontaining a hydrophobic group substantially increases the waterrepellancy of epoxidized precondensates, for example, when the latterare applied to cellulose fibers. A relatively large number of fattyamines are known and can be used in the practice of this phase of theinvention, such as, for example, dodecylamine, tetradecylamine,hexadecylamine, oleylamine and the long chain .polyamines in which aprimary amino group is connected through an alkylene radical to asecondary amino group in which one of the hydrogen atoms is substitutedwith an alkyl group containing 12 to 18 carbon atoms or mixtures of suchalkyl groups. Such amines are prepared, for instance, by reacting fattyamines with acrylonitrile and then hydrogenating to make N-alkyltrirnethylene diamines. The original fatty amines are derived fromcoconut oil, soya bean oil, oleic acid and tallow. One commercial aminewhich is supplied under the name Duomeen O is approximately 80% diamine,has a melting point of approximately -20'26 C., a combined weight of 356to 387, a theoretical molecular weight of 321, and an equivalent weightof 201.

The following examples in which the quantities are stated in parts byweight illustrate the practice of the invention Where such long chainamines are incorporated into the resin.

EXAMPLE XVIII 20 grams of Duomeen O (0.05 mole) and 10 grams oftetraethylene pentamine (0.053 mole) were mixed with 20 grams Epon 828(0.053 mole) and heated to 180 F. The exotherm quickly took this to 250F. When the temperature had dropped to 150 F., 50 grams of isopropylalcohol and 10 grams of Epon 828 were added. The temperature was held at160 F. for 10 minutes until bodying was pronounced and the resin wasthen dissolved in 200 grams of water plus 20 grams of 128% by weighthydrochloric acid. The solution was clear and smooth. The pH was 9, theviscosity was 310 centipoises at 80 F. and 18.2% was total solids. Whenthe solution was diluted to 10%, viscosity dropped to 10 centipoises.

EXAMPLE XIX The procedure was the same as in Example XVIII except that10 grams of formalin was added to the final resin solution and theviscosity rose to 16 centipoises.

EXAMPLE XX 15 grams of tetraethylene pentamine, grams of dodecyl amineand 20 grams of Shell Epon 828 were heated to 120 F. and allowed to gothrough the exotherm (200 F.). The product of the reaction was dissolvedin 50 grams of isopropyl alcohol, grams of Epon 828 were added, and heldat 140 F. for 30 minutes. The solution bodied and just before gelationwas poured into 300 grams of water plus 20 grams of 28% by weighthydrochloric acid.

EXAMPLE XXI The procedure was the same as in Example XX except that 10grams of formalin was added to the final resin solution.

One of the unusual properties of the resins of the invention is theirability to alter cellulose fibers. The resins of the invention contain alarge cation and hence are capable of imparting cationic properties tocellulose fibers and starchy materials. They also contain a reactiveepoxide group which is capable of reacting with cellulose fibers andstarchy materials so that a coating of the resin solution will adhere tosuch substances. Furthermore, the resins of the invention have anaflinity for oil soluble substances Which do not ordinarily adhere tocellulose or starchy materials. Additionally, the resins of theinvention improve the wet and dry strength of products made fromcellulose and other anionic substances.

The following examples illustrate the application of the resin tovarious types of cellulosic materials.

EXAMPLE XXII The resin solution obtained as described in Example VII(b)was mixed with 20 grams of formalin and the solids were adjusted to 12%by weight. In 24 hours the viscosity had risen to 1950 centipoises at F.but the solution was easily dilutable with water.

gram portions of bleached kraft were opened in 1 /2 gallons of water atF. and after the additions of resin solution had been made were dilutedwith 6 gallons of cold water and felted in a sheet machine (12 x 12inches). There was a marked tendency to foam which was controlled byadding /3 cc. of a mixture of decanol and tributyl phosphate. The feltedpads or sheets were then die dried at 50 pounds per square inch (p.s.i.)and 400 F. for 3 minutes. They had an average thickness of 50thousandths of an inch.

One inch wide strips were cut from the pads and tested to determine thenumber of pounds required to break them. The values given below are foran average of four tests. The wet strips were soaked for one hour beforetest.

POUNDS TO BREAK ONE INCH STRIPS A test was also made under the sameconditions adding 2% by weight of a standard wet strengthmelamineformaldehyde resin (Parez 607) to the bleached kraft pulp andthis gave a pad which required 74.9 pounds to break it in the dry and22.3 pounds to break it after soaking for one hour. This example showsthat the resin of the present invention is one of the most effective wetstrength resins available since a 4% by weight treatment gives a wetstrength equalling the dry strength of the bleached kraft pulp. It isparticularly noteworthy that 2% by weight of this resin more thantripled the dry tensile strength of the kraft pulp.

EXAMPLE XXIII The kraft, resin and procedure of Example XXII were used,with 2% by weight of the altering resin added to the stock, followed by10% Epon 828. The stock was not sticky. When die dried it showed 86.2pounds dry tensile per inch and 35 pounds after an hour soak. This isnot an overall improvement over the straight 2% resin of Example XXII,which showed 134 pounds dry and 29.4 pounds wet. However, there wasbetter wet abrasion resistance and a higher degree of water repellency.

EXAMPLE XXIV v The resinous materials of the invention were applied topaper as a tub size in proportions of 0.5% to 5% by weight. Aftersolutions of the resin were coated on hte paper, the paper was dried andthe resultant product had improved wet and dry strength.

From the foregoing examples it will be seen that the oil wettabilityimparted to the surface of anionic fibers, such as cellulose, providesan important property not previously possessed by the cellulose andmakes the re sultant product useful for purposes where cellulose is notsatisfactory as such. Thus, treated cellulose fibers of the presentinvention can be used in making filter paper for cigarettes .to removetars and other noxious substances.

When cellulose or other anionic materials are treated with resins of thetype herein described, the resultant treated product is characterized bythe ability to bond or adhere to a large number of substances whichordinarily will not bond to such anionic materials. Examples of suchsubstances have previously been mentioned and include polystyrene,petroleum resins, oleo-resinous varnishes and polyester resins. Thesematerials are oil soluble and do not ordinarily bond directly tocellulose. It has been very difiicult heretofore, therefore, to applysuch materials to cellulose in a beater treatment where the cellulose isdispersed in an aqueous slurry and the material it is desired to applyis added to the slurry. One type of substance where difiiculty has beenencountered particularly is the polyester resin.

In order to demonstrate the application of the invention tests weremade, as shown by the following examples.

EXAMPLE XXV 20 grams of bleached kraft pulp was opened by mixing in 1500grams of water at a specified temperature and the resin of the inventionadded. The quantities of resin used were ordinarily .5% to by weight ofthe cellulose on a dry basis. Then, with good mixing, 5 grams ofpigmented polyester resin solution was poured into the aqueous slurrycontaining the treated cellulose fiber. For this particular test acommercial uncured thermosetting polyester resin was used known asReichhold Polylite 8039. 300 grams of this resin were mixed with 35grams of pigment paste, 45 grams of xylene and 45 grams of methyl ethylketone.

In each test the fiber and resins were mixed vigorously for at leastminutes. The colored fiber was then examined and rated according to thefollowing scheme. A high number indicates good efiiciency in bonding thepolyester resin to the fiber.

(l) Colored resin is immediately centrifugally thrown to breaker walls.None on fiber.

(2) Colored resin appears in fiber as coarse drops.

(3) Colored resin appears in fiber as fine drops.

(4) Color appears to go smoothly on stock, but 10 minutes mixing showsresin on beaker at stirrer level.

(5) Colored resin appears to go on stock but on pressing and drying apad, color is seen to be weak and under the microscope is found to be infine drops.

(6) Colored resin goes on stock to give a bright smooth color which ismaintained on drying a pad.

In the foregoing test a well known commercial cationic methylol melamineresin rates 4 on the scale given when used at a concentration of 3% byweight of the fibers. It is considered that this resin only does halfwhat is desired. It reduces the charge on the cellulose fiber but doesnot impart oil wettability that is necessary for complete effectiveness.

A typical fatty amine, such as dodecylamine, when used at aconcentration of 3% by weight of the cellulose also rates 4 in the test.This amine, and other similar amines, have a certain directing actionthat will make resins add to an anionic fiber to some extent, i.e., apreliminary good distribution of colored resin on the fiber in the testwill be followed by resin globules reforming and being thrown out on thesides of the beater. It is considered that uncured polyester often actsas a solvent, dissolves the directing material adsorbed on the fiber andthen both leave the fiber. The resins of the invention avoid theseobjections. They are water soluble cations that deposit on the cellulosefiber. They are high enough molecular weight to permit easy adsorptionto take place. They do not dissolve in solvents in the presence ofwater. There is evidence also that they react with cellulose and thusare chemically attached. They carry oil wetting or lipophilic areas toalter the wetting of the fiber as desired.

The Adduct A of Example II(a) and the resin of Example IX were evaluatedin the foregoing test using dif- Temperature of Stock, Degrees F.

Adduct A (Example II(a)) Resin of Example IX Methylol Melamine (Parez607)..- Control whim) wreath reread:

It will be seen from the foregoing results that heating improves theeffectiveness of the resins of Example IX but has no effect on methylolmelamine. All treatments were made with 5% by weight of the resin addedto the cellulose on a dry basis. The same treatment was used formethylol melamine.

The Adduct A (Example II(a)) is a cation and carried lipophilic groups.It is relatively low molecular weight, 753 (by the method of formation)and hard to adsorb. Since a slight excess of diepoxide was used, therecan be a few molecules with active oxirane ring present and these willpolymerize at the higher temperature to give a few molecules at 1128molecular weight units and these account for the activity at 200 F. Theaddition of formaldehyde as in Example IX causes polymerization so theresin is effective at lower temperatures.

EXAMPLE XXVI The test procedure of Example XXV was applied to an alteredcellulose obtained by mixing 2% by weight of the resin of Example X withan aqueous slurry of cellulose fibers, based on the dry weight of thecellulose for five minutes at 70 F. The resultant altered fibers rated6.

EXAMPLE XXVII Cellulose fiber was altered with 1% by weight of the resinof Example VIII without formaldehyde and with formaldehyde.

Resinox 594 was used as a heater addition on altered fiber. This is aliquid (65% total solids) one step phenolic resin. The phenolformaldehyde resin was dissolved in water for this test by adding 10parts NaOH to 100 parts resin solids. This solution was distributed inthe treated fiber by stirring and at 140 F. precipitated by bringing thepH to 6 with dilute hydrochloric acid. The resin addition was 20 partsper 100 parts of cellulose fiber. A clean precipitation with clear whitewater was obtained in each case. The stocks were felted into test padsand dried in a fiat die at 50 p.s.i.

The following test results were obtained:

Breaking 24 Hour Grams Formalin Added to Flexural, Unnotehed Water Resinof Example VIII p.s.i. Izod Impact Pickup. percent It is apparent thatthe methylol groups introduced by formaldehyde into the resin of theinvention improved the strength found in a condensation resin beatertreatment.

EXAMPLE XXVIII The resin of Example III(b) was treated with 14 grams offormalin and when 5% by weight of the resultant resin was added tocellulose in an aqueous slurry at 140 F. the altered cellulose bonded topolyester resin and rated 6 according to the test given in Example XXV.

1 3 EXAMPLE XXIX The resin of Example III('c) when added to cellulose at150 F. in an aqueous slurry using 1.5% of the resin, based on the dryweight of the cellulose, gave a product which readily bonded to apolyester resin and rated 5 according to the test procedure given inExampleXXV. With the addition of grams of formalin to the resin ofExample III(c) and otherwise carrying out the procedure under the sameconditions, the product rated 6 according to the test procedure ofExample XXV.

EXAMPLE XXX 2% by weight of the resin of Example XVI added to an aqueousslurry of cellulose at 70 F. rated 5 according to the test procedure ofExample XXV and 6 after the addition of 10 grams of formalin.

EXAMPLE XXXI The resin of Example XX was treated with 10 grams offormalin. Two parts of this resin was added to white kraft pulp openedin water at 100 F., and after five minutes of mixing the pad was feltedand die dried at 400 F. and 50 p.s.i. This was quite water repellent incontrast with a control pad which instantly blotted up water.

3% of the resin was added to a black colored radio speaker diaphragmstock and made into a speaker cone by felting and drying. This was waterrepellent and when soaked was wet strong. It was considered that theusual lacquer dip could be eliminated with this beater treatment.

EXAMPLE XXXII An aqueous slurry of cellulose and glass fiber frovingswas made at 150 F. at a consistency of 4% by weight fiber from thefollowing:

This was altered to solvent wetting by adding the following resin:

'700 grams diepoxide made by reacting 2 moles of epichlorhydrin with onemole of dihydroxy diphenyl dimethyl methane 700 grams tetraethylenepentamine were mixed, heated to 120 F. and allowed to go through the'exotherm period. After the resin had cooled to 160 F. it was dissolvedin 1700 grams of isopropyl alcohol and 350 grams of Epon 828. Thetemperature was held at 160 F. for minutes until the viscosity build upindicated incipient gelation (lumpy gel masses falling from stirrer).The reaction was then stopped by diluting with a solution of 7000 gramsof water and 700 grams of 28% by weight hydrochloric acid. Afterallowing this to stand 15 minutes, 400 .grams of formalin was stirred inand the resin solution at pH 8.5 was allowed to stand overnight.

A sample of stock taken from the treated beater rated 6, or completelychanged to oil wetting.

The breaker was allowed 10 minutes at 150 F. for thorough adsorption ofthe treating resin. parts by weight of phenolic resin was now added forevery 100 parts of fiber as follows:

-6 pounds of caustic soda was dissolved in 2 gallons of water and pouredinto 93 pounds of Monsanto Resinox 594 (at 65% total solids). One gallonof ethyl alcohol was added and the mixture thoroughly stirred. This wasadded to the breaker and thoroughly mixed. 10% of hydrochloric acid wasadded slowly to a pH of 6. The

phenolic resin precipitated in small particles which were liquid at thistemperature. These solvent soluble liquid particles immediately weretaken up by the altered fiber. The water in the breaker was crystalclear in five minutes.

Distribution of the resin on the fiber was perfect. After 15 minutesdwell, the stock was pumped to a stock chest, being diluted from 4% to1% consistency in the process. The temperature dropped from 150 F. to F.

The stock was pumped to a felting tank and luggage pieces felted and diedried. A 760 gram luggage shell showed 12,400 p.s.i. flexural on theside and 10,500 p.s.i. on the top. Side unnotched Izod impact was 5.5and top Izod 6.1 24 hour water pick-up (on 4 x 4 inch samples, all edgescut) was 20.5% on the side and 20.4% on the top.

In conventional production, luggage shells, which are dipped in varnishand oven cured, run 9000 p.s.i. flexural and 8 unnotched Izod, withabout 50% water pickup in 24 hours. Hence, the altered fiber treatmentis a substantial improvement over conventional production.

When the phenolic resin is run without the treating resin to alter thewetting of the fiber there is a great tendency to foam because of smallparticles of free resin. As the stock is pumped in the system otherresin (which may be on the fiber momentarily after the precipitationprocess) works loose. This collects in the foam and deposits on the topof the molded article. The resin rich surface of the preforms startssticking to the drying dies and the phenolic trials ordinarily last nomore than /2 hour before they no longer can be run.

EXAMPLE XXXIII EXAMPLE XXXIV The resins of the invention can be used toproduce beautifully even colored fibers. 10 pounds of cut sisal fiberwas stirred in 40 gallons of water at F. and 90 grams of theformaldehyde resin of Example IX poured into the water. This wasfollowed by 500 grams of polyester resin (Reichhold 8039) containing 50grams of pigment red polyester paste and catalyzed with 1% benzoylperoxide, /z% cobalt drier and 1% methyl ethyl ketone peroxide. Afterthe stirring had distributed the color evenly on the treated fibers, thetemperature of the water was raised to F. and the polyester resin cured.This eliminated the stickiness of the fiber.

Different color batches were made and mixed. These were dispersed withbeaten white kraft pulp, felted and die dried into phonograph cabinets.

In a similar manner, the process can be used to dye cloth, inparticular, by printing the resins of the invention on cloth, agitatingin an aqueous slurry containing pigmented lipophilic resin and curing,if necessary.

EXAMPLE XXXV In preparing a trash container from molded cellulose fiberwhich was to be left out in the weather, it was found necessaary toimpregnate the die dried preform in 25% catalyzed colored polyesterresin (Reichhold 8039) in an acetone solution. When freshly dipped, thecolor penetrated to the center of the cellulose mat, but on drying thecolor and resin migrated to the surfaces before curing. This left thecenter fibers unprotected and caused failure when the container wasexposed to rain.

Using 2% of the resin of Example XVII on the pulp before formingpractically eliminated the movement of the resin. This is due to themore complete wetting of the fibers and improved affinity for resin. Thewater pickups in a test were reduced from 35% to 25% by this procedure.

1 EXAMPLE XXXVI (a) pounds of southern kraft, 5 pounds of ground wood, 3pounds of sulfite and 2 pounds of cotton linters were opened in a beaterand then, with the roll brushing the bed plate beaten until Williamsfreeness was 120 seconds. 1.25 pounds (dry basis) of the resin ofExample XIX was then added and well mixed with the stock. Cones made byfelting this stock and oven drying it would hold water for two hours(duration of the experiment) without losing form and without theunderside of the cone becoming wet. Without the resin treatment thecones collapsed within 15 seconds when filled with water. The treatedcones when built into radio speakers had the typical response of thelacquer dipped control.

(b) In a second trial the stock was beaten in the same manner and afteradding 1% of the altering resin of Example VIII plus 10 grams offormalin the temperature was taken to 180? F. with a steam hose. At thistemperature it was observed that the fibers took the colored test resinreadily. The stock was cooled to 120 F. and 5 pounds of a 50% totalsolids oleoresinous varnish was poured in. The varnish solvent wasmineral spirits. The solids portion consisted of /a raw tung oil, /3rosin and /3 of a hard petroleum resin. As the stock was stirred, it wasobserved that the varnish went onto the fiber, leaving clear water. Thestock felted without sticking either on the felter or on drying forms.Two hours in the oven at 300 F. or two days air drying were required tocomplete the cure of the varnish, after which the cones were highlywater repellent and wet strong, with a good sound response.

EXAMPLE XXXVII The following cellulose stock was dispersed in a breakerat 145 F.

The stock was altered to oil wetting by adding 2 /2 gallons of reagent(1). Reagent (2) was then added. After this was well mixed, caustic sodadissolved phenolic (3) was added and then precipitated with acid. Thebatch was diluted with cold water and pumped to a stock chest.

A molded luggage shell made from this stock had a density of 0.82 to 0.9gram per cc. flexural top 8700 p.s.i., impact, 5.7, flexural side 8400p.s.i., impact, 5.3, and 24 hour water pickup 33%. This shell held water5 days without weakening or leaking at which time the test was ended.

The reagents (*1), (2) and (3) were made as follows:

(1) 600 grams tetraethylene pentamine was heated with 600 grams Epon 828and allowed to exotherrn. This was dissolved in 1500 grams isopropylalcohol and 300 grams of Epon 828 was added. The solution was held at120 F. for /2 hour until bodied and diluted with water and 600 grams 28%by weight hydrochloric acid to 5 gallons, and 300 grams formalin added.

(2) 7 pounds crude dicyclopentadiene resin Amoco Chemical (Panarez 770)at 70% total solids, and 23 pounds of scrap polystyrene at 44% totalsolids in xylol and naphtha mixed together in equal parts.

(3) 480 grams caustic soda dissolved in /2 gallon of water and stirredwith 16 pounds phenolformaldehyde resin (Resinox 594) and 4 poundsisopropyl alcohol.

The acid precipitation of the phenolic was effected by adding to thebreaker 1450 cc. of 28% by weight hydrochloric acid. Conventionaldefoaming agents (decyl alcohol, tributyl phosphate and Dow Corningantifoam B) were used to control the foaming.

16 The resultant altered cellulose contains 1% altering resin(epoxidized precondensate plus formaldehyde), 3% dicyclopentadiene, 5%polystyrene and 7% phenolic based on the dry fiber.

Reagent (2) does not distribute on the fiber unless reagent (1) is firstused.

EXAMPLE XXXVIII This example illustrates the application of theinvention to the altering of cellulose fiber so that it will have anaflinity for polystyrene.

The cellulose fiber consisted of 20 grams of bleached kraft cellulosewhich was opened to form a slurry by mixing in 1500 grams of water.

The altering resin was prepared by allowing grams of tetraethylenepentamine and 100 grams of Epon 828 to react. The product was thendissolved in 250 grams of isopropyl alcohol and 50 grams of Epon 828 wasadded. The solution was allowed to ripen to incipient gelation at F. Theresultant product was then dissolved in 100 grams of water plus 100grams of 28% by weight hydrochloric acid and 50 grams of formalin wasadded. The product was diluted with water to 10% solids.

4 grams of the altering resin as previously described (2% by weight ofthe cellulose) was mixed with the slurry of cellulose at 120 F. for 5minutes, then 10 grams of polystyrene was added. The polystyrene wascolored and was prepared by mixing 100 grams of a 44% total solidssolution of polystyrene in equal parts of xylol and naphtha with 20grams of xylol, grams of acetone and 5 grams of oil black dye.

The polystyrene was added to the stirred cellulose slurry containing thealtering resin at 120 F. and bonded to the altered cellulose fiberimmediately. It retained its affinity for the cellulose fiber as thetemperature was raised to 180 F. A very uniform product was obtained.

The colored polystyrene will not attach itself to the untreatedcellulose fiber.

EXAMPLE XXXIX The procedure was the same as in Example XXXVIII exceptthat 10 grams of uncured polyester thermosetting resin (Reichhold 8039)was added to the mixing slurry of altered cellulose fiber prior to theaddition of the polystyrene. The polyester resin attached itself to thealtered cellulose fibers immediately and the polystyrene resin readilyattached itself to the polyester resin-altered cellulose fiber as mixingwas continued.

EXAMPLE XL Cellulose in an aqueous slurry was altered as described inExample XXXVIII by adding an epoxidized precondensate and the slurry wasthen treated with 10 grams of polyester resin and 1 gram of tall oilfatty acids. The resultant stock when dried showed a pronounced sizingeffect.

EXAMPLE XLI 710 grams of Epon 828 and 720 grams of tetraethylenepentamine were allowed to react exothermically until the reaction hadsubsided.

1430 grams of the resultant adduct were then dissolved in 1070 grams ofmethyl ethyl ketone and 357 grams of Epon 828 were added giving a resinsolution containing 62.5% total solids. This was allowed to stand orripen at 130 F. for 30 minutes and samples were taken from the ripeningsolution at intervals during this time. 600 gram samples of the ripeningsolution were dissolved in each case in 1500 grams of water to which hadbeen added grams of 28% hydrochloric acid. The resultant aqueoussolutions therefore contained 16.7% resin. The viscosity increased onripening as shown by the following table.

TABLE I In Methyl In Water Ethyl Ketone, Centipoises Sample Centipoisesat 8 F.

at 130 F. (16.7% Total (62.5% Total Solids) Solids Adduct 2d addition A-2d addition minutes 2d addition 12 minutes 2d addition 21 minutes B 2daddti)tion 30 minutes (Clear orn C 2 addition 38 minutes 500 30 D 2daddition 45 minutes 840 34 E {2d addition 51 minutes 1, 350 38 {2daddition 65 minutes 1 Oil range.

TABLE II Formalin:

In water, centipoises at 85 F. (14.8% total solids) F 18 G 28 H 30 I 40J 48 The foregoing resins F to I were found to have cellulose alteringability.

It will be recognized that the invention is susceptible to somevariation and modification in the manner of its practical application.While various types of substances have heretofore been proposed foraltering anionic fibers, such as cellulose, it is believed that thealtering resins prepared in accordance with the present invention areoutstanding in their properties and produce results not heretoforeobtained.

In the foregoing description where reference has been made to polyesterresins, it will be understood that these resins are made by reacting apolyhydric alcohol and a polybasic acid or acid anhydride and containunsaturated components which are capable of cross linking when the resinis cured. Usually at least a portion of the acid component is maleicanhydride. The polyhydric alcohol-polybasic acid composition is added toto 40% by Weight of a monomeric aryl vinyl compound, such as styrene orvinyl toluene. For example, a relatively rigid or non-flexible resin canbe prepared by reacting 2 moles of ethylene glycol with 1 mole ofphthalic anhydride and 1 mole of maleic anhydride for 2 to 4 hours at atemperature of 160 C. in an inert atmosphere such as nitrogen, carbondioxide or illuminating gas and then adding to the resultant product 10to 40% monomeric styrene. The resin in this form is liquid and usuallyhas an acid number around 10 to 50. When this liquid resin is heatedwith a curing catalyst a solid, infusible resin is formed.

Suitable catalysts are the organic peroxides which are soluble in thehydrophobe or resin phase, e.g., benzoyl peroxide, acetylbenzoylperoxide, cumene hydroperoxide, para-tertiary butyl perbenzoated, andother oil soluble oxygen supplying catalysts.

Other ethylene or propylene glycols, including polyethylene andpolypropylene glycols, can be used instead of ethylene glycol providedthey produce water insoluble polyesters. Other dicarboxy acids can beused, e.g., adipic acid is a good flexabilizer.

Instead of styrene other monomeric aryl compounds having an unsaturatedside chain can be employed, e.g., vinyl toluene, vinyl naphthalenes,vinyl ethyl benzenes, alpha methyl styrene, vinyl chlorobenzenes, vinylxylenes, divinyl benzene, divinyl toluenes, divinyl naphthalenes,divinyl xylenes, divinyl ethyl benzenes, divinyl chlorobenzenes,divinyl-phenyl vinyl ethers and diallyl phthalate. Lower boilingmonomers such as vinyl acetate usually are not satisfactory because thereaction which takes place when the resin is cured is very exothermicand the heat would drive off low boiling monomers.

The polyamines used in making the resins of the invention contain atleast two reactive amino groups (i.e., contain at least two aminonitrogens with hydrogen atoms attached). To make altering resins theyshould contain at least four carbons. Polyamines with less than fourcarbon atoms give wet strength resins but not altering resins. Aliphaticpolyamines give the best resins. Aromatic polyamines are preferablyemployed in conjunction with aliphatic polyamines.

The polyepoxide preferably has an epoxide equivalent of 43 to 1000.

The adduct formed initially from the polyamine and the polyepoxide ismade by reacting a polyamine and a polyepoxide in the approximateproportions of two reactive amino groups per epoxy group. Theexothermically formed adduct is preferably further epoxidized toincrease the number of epoxy groups. The additional epoxide groups arepreferably sufficient to give a molar ratio of epoxy to reactive aminogroups of 0.85:1 to 2.511.

In the formaldehyde condensation, the ratio of formaldehyde (either informalin solution, or as formaldehyde gas, or from para-formaldehyde orother formaldehyde liberating compound) is 0.25 mole to 15 moles HCHOper mole of reactive amino groups (e.g., 0.5 mole to 30 moles of HCHOper mole of an aliphatic diamine).

The resins of the invention are usually prepared as thickened solutionsshort of'gel formation. The solutions are usually aqueous solutions andsuch solutions can have varying pHs, for example, pH 2 to pH 12, byadjusting the acid and alkali concentrations with acids and alkaliswhich do not precipitate the resins, e.g., those having monovalentanions and cations, respectively. Non-aqueous solvents can also be usedto dissolve the resins and these solvents can be water miscible, waterimmiscible, or mixtures of water miscible and water immiscible solvents.Examples of such solvents are isopropanol, acetone, methyl ethyl ketone,methyl isobutyl ketone, and mixtures of methyl isobutyl ketone andacetone. The organic solvent solutions can also contain water and acidsor alkalis of the non-precipitating type. Hydrochloric acid solutionsare preferred. These can be either acidic or alkaline because whenhydrochloric acid is used to short stop the second stage epoxidation itis not necessary to reduce the pH below about 9. The alkalinity here isfurnished by the polyamine.

The solids content of the resin solutions can vary widely up to about65% without being too viscous to pour but it is usually preferable touse the resin solutions at a solids content of 10% to 20%.

The preferred resins have a structure derived from the polyepoxideconsisting of alternating aliphatic chains and aromatic nuclei.

To illustrate the manner in which the epoxide equivalent can varydepending upon the molecular weight of the reactants, the resin producedby reacting two moles of tetraethylene pentamine with one mole of Epon828 and a second addition of 0.5 mole of Epon 828 has a calculatedepoxide equivalent of 950. If diethylene tn'amine and butadiene dioxideare used, the epoxide equivalent is 340.

The addition of the formaldehyde has a number of important advantagessuch as (a) increasing the molecular weight; (b) giving a furthercondensation of the molecule on heating after it is adsorbed on thefiber; (c) giving a reactive point for subsequently added condensationresins;

19 and (d) providing hydrophilic areas to prevent dry cleaning of thefiber by solvent dissolved resins.

The anionic water insoluble substances such as cellulose and starch arecharacterized by containing reactive hydroxyl groups. These react withthe epoxy groups of the epoxidized amine to bond the latter to thecellulose or starch, thereby introducing into the latter a cationic(amino) group and a lipophilic group which changes the surface of thecellulose or starch to oil wetting.

The altering of anionic materials and the treatment of the alteredmaterials with non-aqueous anionic and/or non-ionic resins is claimed inmy copending application, Ser. No. 129,517, filed Aug. 7, 1961, laterrefiled as Ser. No. 424,114, filed January 7, 1965. The treatment ofcellulose and starch with various altering resins, including thoseherein described, followed by the subsequent addition of anionic and/ornon-ionic resins and/or pigments is described and claimed in US.application Ser. No. 410,779, filed November 12, 1964, which is acontinuation of Ser. No. 129,516, filed Aug. 7, 1961.

The invention is hereby claimed as follows:

1. A hydrophilic resin which is the product of the reaction offormaldehyde and a hydrophilic epoxidized precondensate of a polyepoxidehaving an epoxide equivalent of at least 43 and a polyamine, said resincontaining at least two equivalents of reactive amino groups for eachepoxide group in the precondensate and additional epoxide sufiicient toprovide free epoxy groups but insufiicient to destroy the hydrophilicproperty of said resin, the quantity of formaldehyde being sufiicient toincrease the viscosity of aqueous solutions of said resin butinsufficient to produce gel formation.

2. A resin as claimed in claim 1 in which said resin contains 0.1 to 0.8equivalent of additional epoxide group.

3. A resin as claimed in claim 1 in which said polyamine contains atleast 4 carbon atoms.

4. A resin as-claimed in claim 1 in which said resin contains at leastone mole of formaldehyde per mole of epoxidized precondensate.

5. A resin as claimed in claim 1 in which said epoxidized precondensatecontains at least 9% by weight nitrogen.

6. A resin as claimed in claim 1 in which said epoxidized precondensatecontains an olefinic unsaturated group bonded thereto.

7. A resin as claimed in claim 1 in which said epoxidized precondensatecontains a hydrocarbon group of 12 to 18 carbon atoms bonded to an aminogroup thereof.

8. A resin as claimed in claim 1 in which said polyamine is apolyethylene polyamine containing two primary amino groups reacted witha polyepoxide having approximately two epoxy groups and an epoxideequivalent of 43 to 1000, in proportions of approximately 2 moles ofsaid polyamine per mole of said polyepoxide and further epoxidized togive a hydrophilic epoxidized precondensate containing free epoxy groupsand containing at least 9% nitrogen.

9. A hydrophilic resin which is the product of the reaction offormaldehyde with a hydrophilic epoxidized precondensate ofapproximately two moles of a polyamine having two primary amino groupsand at least four carbon atoms and one mole of a polyepoxide having anepoxide equivalent of 43 to 1000, said precondensate also having freeepoxy groups sufficient to cause the resultant resin to be adherent tocellulose but insufficient to produce gelation in water, the quantity offormaldehyde being 0.5 to 30 moles per mole of said polyamine.

10. Cellulose containing 0.5 to 5% by weight of a hydrophilic resinwhich is the product of the reaction of formaldehyde and a hydrophilicepoxidized precondensate of a polyepoxide having an epoxide equivalentof 43 to 1000 and a polyamine having at least two amino groups withreactive hydrogen atoms and having more than two carbon atoms, theproportion of said polyamine in said precondensate being equivalent toat least two such reactive amino groups per epoxide group and theproportion of formaldehyde being at least one mole per mole ofepoxidized precondensate, said resin being soluble in a 2.5% by weightaqueous solution of hydrochloric acid.

11. Starch containing 0.5 to 5% by weight of a hydrophilic resin whichis the product of the reaction of formaldehyde and a hydrophilicepoxidized precondensate of a polyepoxide having an epoxide equivalentof 43 to 1000 and a polyamine having at least two amino groups withreactive hydrogen atoms and having more than two carbon atoms, theproportion of said polyamine in said precondensate being equivalent toat least two such reactive amino groups per epoxide group and theproportion of formaldehyde being at least one mole per mole ofepoxidized precondensate, said resin being soluble in a 2.5 by Weightaqueous solution of hydrochloric acid.

12. A cellulose product as claimed in claim 10 in which the wet strengthis enhanced by said resin.

13. A cellulose product as claimed in claim 10 in which said polyaminecontains at least four carbon atoms and said cellulose is renderedcationic and oil wetting.

14. A process for preparing a hydrophilic resin which is soluble in a2.5 by weight solution of hydrochloric acid which comprises reacting apolyepoxide having an epoxide equivalent of at least 43 and a polyaminecontaining reactive amino groups, the proportions of said polyepoxideand said polyamine being suflicient to form a precondensate containingat least two equivalents of reactive amino groups for each epoxidegroup, reacting the resultant precondensate with additional epoxidecapable of introducing 1,2-epoxide groups into the molecule, thequantity of said additional epoxide being sufiicient to provide freeepoxy groups but insuflicient to destroy the hydrophilic property of theresultant resin, further reacting the resultant hydrophilic epoxidizedprecondensate with formaldehyde in an amount sufficient to increase theviscosity of aqueous solutions of the resultant resin but insufiicientto produce gel formation.

References Cited UNITED STATES PATENTS 2,909,448 10/ 1959 Schroeder 26093,026,285 3/1962 Hirosawa et al 260834 3,075,945 1/1963 Kissel 26473,129,133 4/1964 Doyle et al 2602 WILLIAM H. SHORT, Primary Examiner.

E. M. WQODBERRY, Assistant Examiner,

10. CELLULOSE CONTAINING 0.5 TO 5% BY WEIGHT OF A HYDROPHILIC RESINWHICH IS THE PRODUCT OF THE REACTION OF FORMALDEHYDE AND A HYDROPHILICEXPOXIDIZED PRECONDENSATE OF A POLYEPOXIDE HAVING AN EPOXIDE EQUIVALENTOF 43 TO 1000 AND A POLYAMINE HAVING AT LEAST TWO AMINO GROUPS WITHREACTIVE HYDROGEN ATOMS AND HAVING MORE THAN TWO CARBON ATOMS, THEPROPORTION OF SAID POLYAMINE IN SAID PRECONDENSATE BEING EQUIVALENT TOAT LEAST TWO SUCH REACTIVE AMINO GROUPS PER EPOXIDE GROUP AND THEPROPORTION OF FORMALDEHYDE BEING AT LEAST ONE MOLE PER MOLE OFEPOXIDIZED PRECONDENSATE, SAID RESIN BEING SOLUBLE IN A 2.5% BY WEIGHTAQUESOUS SOLUTION OF HYDROCHLORIC ACID.